N-o-nitrophenylpropargyl-carbamate

ABSTRACT

IN WHICH R1, R2 and R4, which may be the same or different, each represents a hydrogen atom or a halogen atom or an alkyl, alkoxy or halogenalkyl radical each having from 1 to 4 carbon atoms or a -NO2 or -SCN group, and R4 and R5, which may be the same or different, each represents a hydrogen atom or an alkyl group having from 1 to 4 carbon atoms, as synergistic agents for insecticidally and/or a acaricidally active substances.   Substituted carbanilic acid propargyl esters of the formula

United States Patent Martin et al.

l l l l Jan. 14, 1975 N -O-NITROPHENYLPROPARGYL- C ARBAMATE Inventors: Henry Martin, Basel, Switzerland;

Georg Pissiotas, Loerrach, Germany; Otto Rohr, Therwil, Switzerland Assignee: Ciba-Geigy AG, Basel, Switzerland Filed: Jan. 2, 1974 Appl. No.: 430,284

Related U.S. Application Data Division of Ser. No. 69,887, Septv 4, 1970, Pat. No. 3.800,037.

Foreign Application Priority Data Sept. 4, 1969 Switzerland 13420/69 U.S. Cl. 260/471 C, 424/300 Int. Cl C07c 125/06 Field of Search 260/471 C References Cited UNITED STATES PATENTS 11/1973 Nyquist et al 260147] c Primary ExaminerLorraine A. Weinbcrger Assistant ExaminerL. A. Thaxton Attorney, Agent, or FirmHarry Falbcr; Frederick H. Rabin [57] ABSTRACT Substituted carbanilic acid propargyl esters ol the lormula in which R,, R and R,,, which may be the same or different, each represents a hydrogen atom or a halogen atom or an alkyl, alkoxy or halogcnalkyl radical each having from 1 t0 4 carbon atoms or a-NO or -SCN 1 Claim, N0 Drawings 1 N-Q-NlTROPHENYLPROPARGYL-CARBAMATE in which R,, R and R which may bethe same or different, each represents a hydrogen atom or a halogen atom or an alkyl, alkoxy or halogenalkyl radical each having from 1 to 4 carbon atoms or a NO or SCN group, and R and R which may be the same or different, each represents a hydrogen atom or an alkyl group having from 1 to 4 carbon atoms.

The alkyl and alkoxy groups which are represented by R,, R R R and R may be substituted or unsubstituted, branched or straight-chained. Suitable alkyl and alkoxy groups are, for example, methyl, ethyl and methoxy groups.

Compounds of special importance are those of the formulae tm-o-o-crt -o cn (n) 2 in each of which R R and R which may be the same or different, each represents a hydrogen, fluorine, chlorine or bromine atom or a methyl, methoxy, CF NO or SCN group.

An especially suitable compound is that of the formula This compound is new and therefore also forms a subject of the invention.

The compounds of the formula I may be prepared according to methods which are, in themselves, known,

for example, by the reaction of an isocyanate of the formula Q c (v11) 2 8 with an alcohol of the formula :4 n0- c -o-ca (vnx) in an inert solvent, for example, benzene, petroleum ether or dimethylformamide,'the substituents R,, R R3, R4 and R5 I I having the same meanings as those specified for formula l.

The compounds defined by the general formula I are capable of increasing the activity of insecticidal and/or acaricidal compounds many-fold (synergism). Surprisingly, it has also been found that when using compounds of the formula I, insects or representatives of the order Acarina, which are resistant to carbamates or phosphoric acid esters, can be rendered completely sensitive to these latter compounds. Suitable insecticidally or acaricidally active substances are, for example, the following compounds:

PHOSPHORIC ACID DERIVATIVES Bis-0,0-dicthylphosphoric acaid anhydride (TEPP) 0,0,0,0-Tetrapropyldithiopyrophosphate Dimethyl( 2,2,2-trichlorol hydroxyethyl )phosphonate (TRICHRORFON) 1,2-Dibromo-l ,2-dichlorothyldimethylphosphate (NALED) 2,2-Dichlorovinyldimethylphosphate FOS) Z-Methoxycarbamyl-lmethylvinyldimethylphosphate (MEVINPHOS) Dimethyl-l-methyl-2-( methylcaroamoyl )vinylphosphate cis (MONOCROTOPHOS) 3-(Dimethoxyphosphinyloxy)-N-methyl-N-methoxycis-croton-amide 3-(Dimethoxyphosphinyloxy)-N,N-dimethylciscrotonamide (DICROTOPHOS) 2-Chloro-2-diethylcarbamoyl-l-methylvinyldime thylphosphate (PHOSPHAMIDON) 0,0-Diethyl-0-2-(ethylthio)-ethylthiophosphate (DEMETON) 0,0-Diethyl-S-2-(ethylthio)-ethylthiophosphate S-Ethylthioethyl-0,0-dimethyl-dithiophosphate (Tl-llOMETON) 0,0Diethyl-S-ethylmercaptomethyldithiophosphate (PHORATE) (DlCHLOR- 7 3-Methyl-4-[dipropargylamino]-phenyl-N- methylcarbamate 3 ,5-Dimethyl-4-[dipropargylamino]-phenyl-N- methylcarbamate 2-[ Allyl-isopropylamino]-phenyl-N- methylcarbamate and 3-[Allyl-isopropylamino ]-phenyl-N- methylcarbamate.

CHLORINATED HYDROCARBONS y-Hexachlorocyclohexane [Gammerxane;Lindane;

'yHCH] l,2,4,5,6,7,8,8-Octachloro-3a,4,7,7a'-tetrahydro- 4,7-methyleneindane [Chlordan] 1,4,5 ,6,7,8 ,8-Heptachloro-3a,4,7,7a-tetrahydro-4,7-

methyleneindane [Heptachlor] l,2,3,4,10,10-Hexachloro-1,4,4a,5,8,8a-hexahydroendo-l,4-exo-5,8-dimethanonaphthalene [Aldrin] l ,2,3,4,10,10-Hexachloro-6,7-epoxyl,4,4a,5 ,6,7,8,8a-octahydro-exol ,4-end-5,8- dimethanonaphthalene [Dieldrin] ditto, endo-endo- [Endrin] 6,7,8,9,10,10-Hexachloro-l ,5,5a,6,9,9a-hexahydro- 6,9-methano-2,3,4 benzo[c]-dioxa-thiepene-3- oxide [Endosulfan] Chlorinated camphor [Toxaphen] Decachloroctahydrol ,3 ,4-metheno-2H-cyclobuta[c d] pentalen-Z-one Dodecachloroctahydro- 1 ,3 ,4-methenol H- cyclobutalc d]pentalene [Mirex] Ethyl-1 ,1a,3,3a,4,5,5,511,5a,6-decachloroctahydro- Z-hydroxy-l ,3,4-metheno-lH-cyclcobuta[c d]pentalene-Z- laevulinate Bis(pentachloro-2,4-cyclopentadien-l-yl) Dinoctone 1,1,l-Trichloro-2,2-bis(p-chlorophenyl)ethane [DDT] Dichlorodiphenyl-dichloroethane [TDE] Di(p-chlorophenyl)-trichloromethylcarbinol [Dicofol] Ethyl-4,4-dichlorophenylglycollate late] Ethyl-4,4-dibromobenzylate [Bromobenzylate] Isopropyl-4,4-dichlorobenzylate 1,1 l -Tric hloro-2,2 bis(p-methoxyphenyl )ethane [Methoxychlor] Diethy]-diphenyl-dichloroethane Decachloropentacyclo(3,3,2, 0 0 0 ")decan- 4-one [Chlordecon].

[Chlorobenzy- NITROPHENOLS AND DERIVATIVES 4,6-Dinitro-6-methylphenol Na salt [dinitrocresol] Dinitrobutylphenol-2,2,2-triethanolamine salt 2-Cyclohexyl-4,6-dinitrophenol [Dinex] 2-( l-Methylheptyl)-4,6-dinitrophenyl-crotonate [Dinocap] 2 scc.-Butyl-4,6-dinitrophcnyl-3-methyl-butcnoate [Binapacryl] 2 sec.-Butyl-4,6-dinitrophenyl-cyclopropionate and 2 sec -Butyl-4,6-dinitrophenyl-isopropyl-carbonate [Dinobuton] VARIOUS SUBSTANCES Sabadilla Rotenone Cevadine Veratridine Ryania Pyrethrin 3-Allyl-2-methyl-4-oxo-2-cyclopentenl -ylchrysanthemumate (Allethrin) 6-Chloropiperonyl-chrysanthemumate (Barthrin) 2,4-Dimethylbenzyl-chrysanthemumate (Dimethrin) 2,3,4,5-Tetrahydrophthalimidomethylchrysanthemumate (5-Benzyl-3-furyl)-methyl-2,2-dimethyl-3-(2- methylpropanyl) cyclopropanecarboxylate Nicotine Bacillus thuringiensis Berliner Dicyclohexylcarbodiimide Diphenyldiimide [azobenzene (sic)] 4-Chlorobenzyl-4-chlorophenylsulphide [Chloroben side] Creosote oil 6-Methyl-2-oxo-l,3-dithiolo-[4,5-b]-quinoxaline [Quinomethionate] (l)-3-(2-Furfuryl)-2-methyl-4-oxocyclopent-2- enyl(l)-(cistrans)chrysanthemummonocarboxylate [Furethrin] 2-Pivaloyl-indane-l ,3dione [Pindon] 2-Fluorethyl(4-bisphenyl)acetate 2-Fluoro-N-methyl-N( lnaphthyl)-acetamide Pentachlorophenol and salts 2,2,2-TriChloro-N-(pentachlorophenyl)-acetimidoyl chloride N-(4-Chloro-2 methylphenyl)-N,N-dimethylformamidine (Chlorphenamidine) 4-Chlorobenzyl-4-fluorophenyl-sulphidc benside) 5 ,6-Dichl0ro-l -phenoxycarbanyl-2-trifluoromethylbenzimidazole (Fenosaflor) Tricyclohexyl-stannic-hydroxide 2-Thiocyanatoethyl-lauric acid ester B-Butoxy-B'-thiocyanatodiethyl-ether lsobornyl-thiocyanatoacetate p-Chlorophenyl-p-chlorobenzenesulphonatc (Ovex) 2,4-Dichlorophenyl-benzenesulphonate p-Chlorophenyl-benzenesulphonate (Fenson) p-Chlorophenyl-2,4,5-trichlorophenylsulphone (Tetradifon) p-Chlorophenyl-2,4,5-trichlorophenylsulphide (Tetrasul) Methyl bromide p-Chlorophenyl-phenylsulphone p-Chlorobenzyl-p-chlorophenylsulphide (Chlorobcnside) 4-Chlorophenyl-2,4,5-trichlorophenylazosulphide 2(p-tert.-Butylphenoxy)-l-methylethyl-2-chloroethyl-sulphite 2(p-tert.Butylphenoxy)cyclohexyl-Z-propinyL sulphite 4,4'-Dichloro-N-methylbcnzenesulphonzmilidc N-(Z-Fluoro-l ,1,2,Z-tetrachloroethylthio)- methanesulphonanilidc Fluoro- 2-Thio-l ,3-dithiolo-( 4,5-6 )quinoxalinc ('lhioquinox) Chloromethyl-p-chlorophenylsulphone (lauseto (sic!) new) Such synergistically active mixtures can preferentially be employed against all harmful insects, for example against aphids, such as the green peach aphid (Myzus persicae), and the black bean aphid (Doralis fabae); scale insects lice such as Aspidiotus hederae, Lecanium hesperidium, Pseudococcus maritimus; Thysanoptera such as Hercinothrios femoralis, and bugs such as the beet bug (Piesma quadrata) or the bed bug (Cimex lectularius), caterpillars, such as Plutella maculipennis and Lymantria dispar; weevils such as the granary weevil (Calandra granaria) or the Colorado beetle (Leptinotarsa decemlineaza), but also varieties which live in soil, such as wireworms (Agriotes sp.) or cockchafer grubs (Melolontha melolontha); cockroaches, such as the German cockroach (Blattella germanica); Orthoptera, such as the cricket (Gryllus dmesticus); termites, such as Beticulitermes; Hymenoptera, such as ants; Diptera, such as the vinegar fly (Drosophila melanogaster), the Mediterranean fruit fly (Ceratitis capitata), the housefly (Musca domestica), and gnats, such as the yellow fever mosquito (Aedes aeym)- The use of this synergistic mixture is also especially effective in combatting representatives of the order Acarina such as for example Eulaelaps, Echinolaelaps, Laelaps, l-laemogamasus, Dermanyssus, Ornithonyssus, Allodermanyssus, in particular Allodermanyssus sanguineus, Pneumonyssus, Amblyomma, Aponomma, B0- ophilus, Dermacenter, Haemophysalis, Hyalomma, 1x0- des, Margaropus, Rhipicephalus, Ornithodorus; Otobius, Cheyletidae, for example Cheyletus, Psorergates, Demodicidae, Trombiculia'ae, for example Trombicula, Eutrombicula, Schongastia, Acomatacurus, Neoschongastia, Euschongaslia, Sarcoptiformes for example N0- toedres, Sarcoptes, Knemidokoptes, Psaroptidae, for example Psoroptes, Chorioptes, otodectes 0r Tetranychidae, for example Tetranychus telarius; Tetranychus urticae and the like.

The mixtures can either be used by themselves or together with suitable carriers and/or additives.

Suitable carriers and additives can be solid or liquid and correspond to the substances which are customary in formulation technology, for example, natural or regenerated mineral substances, solvents, dispersing agents, wetting agents, adhesives, thickeners, binders or fertilisers.

Such preparations can be employed in the form of solutions, emulsions, suspensions, granules or dusting agents. The methods of application depend on the end uses and must ensure that the active substance can be finely distributed.

The content of active substance in the preparations described above is between 0.1 and 95%. At the same time it should be mentioned that in the case of application from aircraft or by means of other suitable application instruments, concentrations of up to 99.5% or even a pure active substance may be employed.

To manufacture solutions, it is possible to employ solvents, especially alcohols, for example ethyl alcohol or isopropyl alcohol, ketones, such as acetone or cyclohexanone, aliphatic hydrocarbons, such as kerosene, and cyclic hydrocarbons, such as benzene, toluene, xylene, tetrahydronaphthalene and alkylated naphthalenes, and also chlorinated hydrocarbons, such as tetrachloroethane, ethylene chloride, and finally also mineral and vegetable oils or mixtures of the above mentioned substances.

Aqueous preparations are preferably dispersions. The compounds of formula (I) and the active substance, as such or in one of the abovementioned solvents, are homogenised in water, preferably by means of wetting agents or dispersing agents. Amongst cationic dispersing agents, quaternary ammonium compounds may be mentioned an example, and amongst anionic dispersing agents, soaps, aliphatic long-chain sulphuric acid monoesters, aliphatic-aromatic sulphonic acids and long-chain alkoxyacetic acids may for example be mentioned; amongst non-ionic dispersing agents, polyglycol ethers of fatty alcohols or ethylene oxide condensation products with p-tert. alkylphenols may be mentioned. On the other hand, it is also possible to manufacture concentrates consisting of active substance, synergistic agent or dispersing agent and optionally solvents. Such concentrates can be diluted before use, for example with water.

Dusting agents can be manufactured by mixing or conjoint grinding of the active substance and the synergistic agent with a solid carrier, Possible carriers are for example: talc, diatomaceous earth, kaolin, bentonite, calcium carbonate, boric acid or tricalcium phosphate, but also wood flour, cork powder, charcoal and other materials of vegetable origin. The substances can also be absorbed on the carriers by means of a volatile solvent. Pulverulent preparations and pastes can be rendered capable of suspension in water, and usable as spraying agents, by the addition of wetting agents and protective colloids.

In many cases the use of granules for uniformly releasing the active substance-synergistic agent combinations over a longer period of time is of advantage. These granules can be manufactured by dissolving the active substance in an organic solvent, absorbing this solution by a granular mineral, for example attapulgite or SiO and removing the solvent. They can also be manufactured by mixing the active substances of formula l with polymerisable compounds, after which a polymerisation is carried out which leaves the active substances unaffected, with the granulation being carried out whilst the polymerisation is still proceeding.

The following Examples illustrate the invention.

EXAMPLE 1 Manufacture of N-o-nitrophenylpropargyl-carbamate 41 g of o-nitrophenylisocyanate in ml of dimethylformamide were added dropwise to 14 g of propargyl alcohol in 75 ml of dimethylformamide, at 25C, whilst cooling. The reaction mixture was stirred at room temperature for approx. 10 to 12 hours and subsequently poured into ice water. The crystals of the compound of formula N0 (Active substance 110. 1)

which precipitated were recrystallized from benzene/- petroleum ether. Melting point 7779C. The following compounds of formula EXAMPLE 2 Nit-cu Dusting Agents 0CH Equal parts of a mixture of active substance and syn- I ergistic agent and of precipitated silica are finely 5 I 2 d Dustmg agents preferably contaimnig l 6 c. 0.085 of compound (A) and 0.08y of compounds of active substance, can be manufactured therefrom by NOS 1 2, 3, 6, 7 9 l2, 15 20, 45 49, 53, 55, 57 mixing with kaolin or talc. and 78 Spraying Powder Compound 0.08M r (Hlily of (A) (ma at A and 10 No. synergistic 0.08 of To manufacture a spraying powder, the following agent synergistic components are for example mixed and finely ground: 14cm 50 parts of a mixture of active substance and syner- 1 0 I7 92 gistic agent 2 0 17 65 20 parts of highly adsorbent silica 2, 25 parts of Bolus alba (Kaolin) 7 0 I7 40 1.5 parts of sodium l-benzyl-Z-stearylg benzimidazole-6,3-disulphonate and 15 0 I7 45 3.5 parts of a reaction product of p-tert. octylphenol 0 45 0 l7 so and ethylene oxide. 49 0 i7 53 0 I7 65 Emulsion Concentrate 8 22 The easily soluble mixture of active substance and 78 0 i7 75 synergistic agent can also be formulated as an emulsion concentrate in accordance with the following instruc- 25 EXAMPLE 4 tion: I

20 parts of a mixture of active substance and syner- 1 g f ;f g;gingg sg jgfig compound gistic agent, 5 70 parts of xylene and O-C-NHCH 10 parts of a mixture ofa reaction product of an alkyl l phenol with ethylene oxide and calcium 0 m"; limmcarb dodecylbenzenesulphonate are mixed. On dilution with water to the desired concentration, a spraya- 2 ble emulsion results.

Granules 7.5 g of a mixture of active substance and synergistic agent are dissolved in 100 ml of acetone and the acecarba'ryl (3) tone solution thus obtained is added to 92 g of granular attapulgite. The whole is well mixed and the solvent is 40 stripped off in a rotary evaporator. Granules containing 2 7.5 of active substance are obtained. 000mm} 5 EXAMPLE 3 home" propomr (c) Test for Synergistic Action For this test, female house flies aged from 2 to 5 days were used. Before the start of the test, the flies were 0H '5 sorted as to gender under CO narcosis, and the females were placed in groups of 10. The flies, which 0 N were kept motionless with CO were treated with a disn penser which on pressing the button each time releases fz j i l microlitre of the solution of the test substance in ace- "0 cflcfl tone. After the treatment, the flies were placed in groups of 10 in Petri dishes into which a cottonwool pad impregnated with honey water had been intro- QCQNHCIL duced for the flies to feed on. After 24 hours the test was evaluated by counting the flies which could no '5 longer move. The results quoted in the table represent "K i average values for the percentage destruction from CHZCFI CH four repeat tests.

The following were each used per fly (weight of one fly 20 mg (average value)): K

a. 0.087 of each of the compounds Nos. 1, 2, 3, 6, 7, P-S-CH-CQQC2HF mflaunon (P) 9, 12, I5, 20, 45, 49, 53, 55, 57 and 7s 01: 0

b. 0.08 of the compound of formula CH3) z r 0.17 Compound No. 1+

\1) 0 1') (C) X0 o c cc N\C phosphamldon (G) d) 0.27 Compound No.1 0 on. I l H 2 5 7 (D) 10 (H3 0.27 Compound No. 1+ 5 02 (D) 90 c) 0.087 Compound No. 0 0.08 (E) 0.087 Compound No. 1+ 0.08 (E) xx O=C C*OCH. f) 0.67 Compound No. 1 0 CH 0 0 I j l 0.6 (F) 15 PscH trN methidathion (11) 3-? W H 1 CH 7 (f) 7,

j g) 0.1 Compound No. 1 0

0.1 (G) 3 0.1 Compound No. 1+ 0.1 (G) 78 pyrcthrum 7 (I) 15 h) 0.17 Clgmpound No. 1 0 0.1 l5

- was earned out analogously to example 3. QT I 99 The results listed in the table represent average vali) 0.07 Compound No l 0 0.07 (1) )0 ues of the percentage destructlon of female house flles, Omy Compound N04 H from two repeat experlments. 0.07 (I) 29 We claim: a) fxy 1 g l. The compound of the formula 0.327 Compound No. 1+ 0 0.32 (A) 84 b) 008 Compound No. 1 0 1 a c ca 0108 (B) 5 v 0.087 Compound No. 1+ 0.087 (B) 95 H0 c) 0.1 Compound No. 1 0 

